Environmental risk evaluation of the use of mine spoils and treated sewage sludge in the ecological restoration of limestone quarries

The ecologic restoration criteria in areas degraded from extraction activities require making use of their mine spoils. These materials do not meet fertility conditions to guarantee restoration success and therefore, need the incorporation of organic amendments to obtain efficient substratum. Reducing the deficiencies in the organic material and restoration material nutrients with the contribution of treated sewage sludge is proposed in this work. This experiment was based on a controlled study using columns. The work was conducted with two mine spoils, both very rich in calcium carbonate. The first mineral, of poor quality, came from the formation of aggregates of crushed limestone (Z). The other residual material examined originated in limestone extraction, formed by the levels of interspersed non-limestone materials and the remains of stripped soils (D). Two treatments were undertaken (30,000 and 90,000 kg/ha of sewage sludge), in addition to a control treatment. The water contribution was carried out with a device that simulated either short-duration rain or a flooding irrigation system in order to cover the surface and then percolate through the soil. The collection of leached water took place 24 h after the applications. Different parameters of the leached water were determined, including pH, electrical conductivity, nitrate anions, ammonium, phosphates, sulphates and chlorides. The values obtained for each irrigation application are discussed, and the nitrate values obtained were very elevated.     

Composition, P-T parameters, and metasomatic transformations of mafic schists of the Svyatoi Nos Peninsula, Eastern Baikal Area

The paper reports data on rock and mineral compositions from the Svyatonosskaya Formation, which is a continuation of the Ol’khon Series in the northern part of the Svyatoi Nos Peninsula, eastern shore of Lake Baikal. The pyroxene-amphibole-plagioclase schists (metagabbro) are replaced there by the garnet-biotite-quartz assemblage, which was formed, according to the data of various geothermometers and calculations by the THERMOCALC computer program, under conditions corresponding to the transition from the granulite (848–811°C) to high grades of the amphibolite (715–670°C) facies under high pressures (8.7 ±1.6 kbar). In petrogenetic grids, these conditions fall onto the line of the onset of eclogitization. In nature these rocks are a continuation of the Chernorudskaya-Barakchinskaya zone of elevated pressures in the Ol’khon area. The metasomatic rocks were formed simultaneously with strike-slip faulting, when coupled zones of relatively high-(eclogite-like) and low-pressure (quartzite-marble melange) developed at the inflow of SiO₂ and K₂O and the removal of MgO and CaO. Analogous compositional changes in gneisses and schists in tectonic extension zones in Ol’khon Island and neighboring areas occurred during the development of migmatites. The migmatization of the gneisses was likely coupled with the garnetization of mafic schists in high-pressure zones and the formation of eclogite-like rocks replacing marbles. The accompanying graphitization of this block suggests that the metasomatic fluid had a hydrocarbon-hydrogen composition.     

Diamond formation in sulfide pyrrhotite-carbon melts: Experiments at 6.0–7.1 GPa and application to natural conditions

Experiments at 6.0–7.1 GPa and 1500–1700°C were carried out to explore the boundary conditions of diamond nucleation and growth in pyrrhotite-carbon melt-solutions. Pyrrhotite is one of the main sulfide minerals of the pyrrhotite-pentlandite-chalcopyrite assemblage of mantle rocks and primary inclusions in diamond. Solutions of carbon in sulfide melts oversaturated with respect to diamond at the expense of the dissolution of starting graphite (thermodynamically unstable phase) are formed owing to the difference between the solubilities of graphite and diamond, which increases under the influence of temperature gradients in experimental samples. We determined the fields of carbon solutions in pyrrhotite melt showing labile and metastable oversaturation with respect to diamond, which correspond to the spontaneous nucleation of the diamond phase and diamond growth on seeds, respectively. The linear growth rate of diamond in sulfide-carbon melts is rather high (on average, 10 μ/min during the first 1–2 min from the onset of spontaneous crystallization). The nucleation density is estimated as 180 grains per cubic centimeter. Diamonds crystallized from sulfide melts show octahedral and spinel twin shapes. Diamond polycrystals were synthesized for the first time from a sulfide medium as intergrowths of skeletal (edge) or “cryptocrystalline” microdiamonds, from 1 to 100 μm in size, their spinel twins and, occasionally, polysynthetic (star-shaped) twins. During diamond growth from sulfidecarbon melts on smooth faces of cuboctahedral diamond seeds synthesized in metal systems, smooth-faced layer-by-layer step-like growth was observed on their octahedral (111) faces, whereas growth on the (100) cubic faces produced rough-surfaced layers of intergrown micropyramids, whose axes were oriented normal to the (100) face. The obtained experimental results were applied to the problem of diamond genesis under the conditions of the Earth’s mantle in the framework of the model of carbonate-silicate parental melts with blebs of immiscible sulfide melts.     

Liquid immiscibility in deep-seated magmas and the generation of carbonatite melts

This paper reviews the results of investigations of melt inclusions in minerals of carbonatites and spatially associated silicate rocks genetically related to various deep-seated undersaturated silicate magmas of alkaline ultrabasic, alkaline basic, lamproitic, and kimberlitic compositions. The analysis of this direct genetic information showed that all the deep magmas are inherently enriched in volatile components, the most abundant among which are carbon dioxide, alkalis, halides, sulfur, and phosphorus. The volatiles probably initially served as agents of mantle metasomatism and promoted melting in deep magma sources. The derived magmas became enriched in carbon dioxide, alkalis, and other volatile components owing to the crystallization and fractionation of early high-magnesium minerals and gradually acquired the characteristics of carbonated silicate liquids. When critical compositional parameters were reached, the accumulated volatiles catalyzed immiscibility, the magmas became heterogeneous, and two-phase carbonate-silicate liquid immiscibility occurred at temperatures of ≥1280–1250°C. The immiscibility was accompanied by the partitioning of elements: the major portion of fluid components partitioned together with Ca into the carbonate-salt fraction (parental carbonatite melt), and the silicate melt was correspondingly depleted in these components and became more silicic. After spatial separation, the silicate and carbonate-silicate melts evolved independently during slow cooling. Differentiation and fractionation were characteristic of silicate melts. The carbonatite melts became again heterogeneous within the temperature range from 1200 to 800–600°C and separated into immiscible carbonate-salt fractions of various compositions: alkali-sulfate, alkali-phosphate, alkali-fluoride, alkali-chloride, and Fe-Mg-Ca carbonate. In large scale systems, polyphase silicate-carbonate-salt liquid immiscibility is usually manifested during the slow cooling and prolonged evolution of deeply derived melts in the Earth’s crust. It may lead to the formation of various types of intrusive carbonatites: widespread calcite-dolomite and rare alkali-sulfate, alkali-phosphate, and alkali-halide rocks. The initial alkaline carbonatite melts can retain their compositions enriched in P, S, Cl, and F only at rapid eruption followed by instantaneous quenching.     

Crystallization of authigenic carbonates in mud volcanoes at Lake Baikal

This paper presents data on authigenic siderite first found in surface sediments from mud volcanoes in the Central (K-2) and Southern (Malen’kii) basins of Lake Baikal. Ca is the predominant cation, which substitutes Fe in the crystalline lattice of siderite. The enrichment of the carbonates in the ¹³C isotope (from +3.3 to +6.8‰ for the Malen’kii volcano and from +17.7 to +21.9‰ for K-2) results from the crystallization of the carbonates during methane generation via the bacterial destruction of organic matter (acetate). The overall depletion of the carbonates in ¹⁸O is mainly inherited from the isotopic composition of Baikal water.     

General characteristics of the geochemical evolution of silicic melts during the development of massive sulfide magmatic ore systems: Evidence from the investigation of melt inclusions

The investigation of melt inclusions in the minerals of volcanic rocks from the massive sulfide deposits of Siberia and the Urals revealed some specific features in the development of their magmatic ore systems. It was shown that the petrochemical and rare earth element compositions of melt inclusions reflect the geodynamic conditions of their formation: island arc conditions for the massive sulfide deposits of Rudny Altai, eastern Tuva, and the Salair Range and a back arc basin environment for the Yaman-Kasy deposit. The silicic melts of inclusions from the volcanic rocks of massive sulfide deposits show some specific features with respect to the contents of volatile components. In all of the ore deposits studied, fluorine content was always low (0.03–0.08 wt %), whereas chlorine content (0.13–0.28 wt %) was higher than the average value for silicic melts (0.17 wt %). There is a strong differentiation of water content in melt inclusions, both between deposits and between various volcanics from a single deposit. Ore-bearing melts show the highest water contents of 3.34–4.07 wt %. High Cu contents in the silicic melts of the Yubileinoe and Kyzyl-Tashtyg deposits (up to 7118 and 3228 ppm, respectively) may indicate the affinity of some ore components to particular silicic magmas. This is supported by the elevated contents of Cu in the porphyry Cu deposits of Romania (Valea Morii), Mongolia (Bayan Ula), and Bolivia. On the other hand, the silicic melts of inclusions from the molybdenum-uranium deposit of the Strel’tsovka ore field show high contents of another group of ore components (U and F).     

Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.